Catalyst and method of preparing same



Patented Oct. 20, 1953' UNITED STATES" OFFICE CATALYST AND METHOD OF PREPARING SAME Jack F. Eberle, Bartlesville, 0kla., assignor to Phillips Petroleum Company, a corporation of Delaware No Drawing. Application January 4, 1949,

Serial No. 69,112

22 Claims. (01. 252-435) bon effluent of an alkylation process in which a fluorine-containing catalyst is employed. In one aspect the invention relatesto the conversion of organic fluorine compounds to hydrogen fluoride and the corresponding organic residue. The invention further relates to the recovery of hydrogen fluoride liberated by such reaction.

This application is a continuation-in-part of my copending application Serial No. 694,130,filed August 30, 19%,now abandoned. I

In the manufacture of hydrocarbons by processes in which a fluorinecontaining catalyst is I boiling hydrocarbons to produce motor fuel having ahigh octane rating, and are efiected in the presence of catalysts comprising gone or more of such inorganicfiuorine compounds as hydrofiuoric acid, boron trifluoride and the like. Al-

eral reactants used in the conversion process.

However, some of the organic fiuorine'compounds do have higherboiling points than the reactants and the boiling points of the higher-boiling fluorides correspond tothe boiling points of the conversion products. As a result, these organic fluorine compounds Will be found in the various hydrocarbon fractions in subsequent separation processes forseparating and refining the prodpots, and in many instances the organic fluorine presence of moisture.

2 compounds tend to accumulate in the high-boiling hydrocarbon fractions. These fluorides tend to decompose at elevated temperatures, such as those employed in fractional distillation of the hydrocarbon mixture, thereby forming hydrofluoric acid which is corrosive, especially in the In gaseous mixtures of hydrocarbons they may thus cause corrosion of treating equipment in liquid hydrocarbon mixtures, and especially motor fuels, they are undesirable for similar reasons that are obvious and because they reduce the antiknock value of the fuel.

Consequently, it is highly desirable and ofte essential to minimize the accumulation of the organicfluorine compounds, or to remove them from the hydrocarbon effluent of such processes as described. Various methods have been used to remove the organic fluorine compounds from the hydrocarbon efliuent. For example, in the alkylation of low-boiling paraffins in the presence of a hydrofluoric acid alkylation catalyst the alkylation effluent is passed to a separator wherein a liquid hydrocarbon-rich phase and a liquid hydrogen fluoride-rich phase are formed. The liquid hydrocarbon richphase is passed from the separator to a distillation column wherein dissolved hydrogen fluoride is removed as anfoverhead azeotropic mixture with light hydrocarbons. The bottom fraction contains the alkylate productand also minor proportions of organic fluorine compounds-which are undesirable as previously mentioned. In the usual practice the bottom fraction from this distillation is treated to remove the organic fluorine compounds. Such treatments comprise contacting the bottom fraction With a suitable sorption material which selectively sorbs the organic fluorine compounds,

.or contacting the bottom fraction with a catation agents which are suitable for converting the organic fluorine compounds include various fluoconsidered. As a result of some of the fluorine compounds, especially the high-.hoiling organic, fluorine compounds, remaining in the hydrocarv. bon fraction, the hydrocarbon stream becomes corrosive as a result of the accumulation of; the organic fluorine compounds in the bottom fractions from various fractional distillations subse- 4 fluorine compound with a catalytic agent according to one embodiment of this invention, the organic fluorine compound is decomposed into hydrogen fluoride and the corresponding organic radical, The decomposition of the organic fluorine compound is an equilibrium reaction, as evidenced by the following typical reaction equation:

Alkyl fluoride Olefin+HF Once such an equilibrium is established in the presence of a catalyst no further decomposition of the organic fluorine compound takes place unless one of the products of decomposition is requent to the conventional organic fluorine come. j.

pound-removal process.

Therefore, it is much to stantially all of the organic fluorine compounds from the hydrocarbon stream in order to prevent corrosion of subsequent equipment by concentration of the organic fluorine compounds in the bottom fractions in the various fractional distillahis.

Moreovensince the fluorine combined as the organic fluoride represents over a period of time, a substantial loss "of hydrofluoric acid catalyst in a conversion process such as alkylation, the recovery of the fluorine as hydrogen fluoride would amount to a substantial saving in costs Q at on and m t r There are other known processes in which gaseous or liquid materials containing minor amounts of" organic fluorine compounds are i und. and e r nt invention. m y be a p to the treatment of; such materials or streams. examples may be mentioned the deliberate formation of organic fluorine compounds, particllla lr t e awil n alihha u n m.- which are formed by reacting hydrocarbon o ch orinated yd carbons i el enfluq ne or h r en fluo ide u r s e c ndi i ns Certa n p oduc and. r si l t s in h. p se mar carry o anic l c bine flu r ne in. amounts. an ng usu from methi than 5 P r en do to. ra es,

ob ec f. this venfiiqnis o Provid a ew and mpr ved defl qrinatipn. a ys eeqtlie ob ec s. e Pr d a aly t e u in effecting various organic conversions.

A further object of the invention is to provide a novel method for the preparation of catalysts. 7 It is a further object to increase the efficiency of a dehydrofiuorination catalyst for the removal of; organic fluorine compounds from a hydrocarbon effluent of' a hydrocarbon conversion process.

Further objects and advantages of the invention will be apparent toone skilled in the. art, from the. accompanying. disclosure and. discussion. In accordance with certain aspects of this in ent oni. lu r n c mpou s. an e s bstantia l remq ed rom a fl id miatureq ta nine he am contacting the fluidmixture with a novel catalytic agent which decomposes the. fluorine com to be e. r en uor de an w t a Sui b e sorpt on. me iu whi h is. a a e of plbi l the ib rate h dr sen uor dc- In. o tacting an organic mixture containing an organic moved, such as the olefin or the hydrogen fluoride. If one or both of the decomposition products are removed, t he decomposition reaction of the organic fluorine compound will proceed toward completion and thus decompose substantially all of the organic fluorine compound. Consequently, the organic mixture containing the organic fluorine compound is contacted either simultaneously or alternately with the novel catalytic defluorination agent of the invention and with a suitable sorption medium. The removal of the hydrogen fluoride by the sorption medium upsets the decomposition equilibrium and permits further catalytic decomposition of the organic fluorine compound.

I have found that catalysts effective for dehydrofluorinations and other conversions, having unusually high activity and long life, are obtained if certain metals (if necessary having a coating of metal compound reactible with acid) are treated with a strong inorganic oxygen-containing acid whose anhydride is relatively nonvolatile, particularly phosphoric acid, preferably followed by heating the resulting material at elevated temperatures. The preferred metal is aluminum; cadmium, zinc, and copper may, however, be used if desired, with especially good results. Any of the metals from magnesium to silver, both inclusive, in the Electromotive Force Series of Elements as compiled by Giles B. Cooke, Handbook of Chemistry and Physics, Chemical Rubber Publishing 00., 30th edition (1947), page 1439 may be employed. The preferred group of metals is composed of those from aluminum to trivalent iron, both inclusive, all of which are above H2, in said Electromotive Force Series, viz. Al, Be, U, Mn, Zn, Cr, Ga, Cd, In, Tl, Co, Ni, Sn, Pb, and Fe. However, the metals mentioned specifically hereinabove, viz. aluminum, cadmium, zinc and copper, are preferred. Of course the elements Te, S, As, 02, and I2 appearing within the named groups in said series are not; included in the scope of this invention, being nonmetals. The treated metals are preferably used in a relatively finestate of division, such as shot, shavings, filings, short pieces. of wire, powder, etc. In case powdered material is used it is suspended in the liquid or gaseous hydrocarbon material to. be treated, in accordance with techniques analogous to those utilized in the art of fluidcatalytic cracking. Furthermore, mixtures of two or more metals asv disclosed in my copendmg application Serial No. 6373169 filed De,- oe nber- 2-6, 1945;, which matured to U. S. Patent fl L Q Sep m r 19 9.. m y b ate with phosphoric or other acid of the class described and employed in accordance with the invention, The phosphoric acid used in, treating the metal or metals preferably has an acidity (I'LKPOIL) of at least '75, per cent, and more, do.- sirably, approximately per cent. Other suit- 'tive with phosphoric acid and the like.

cess acid without washing. Preferably the thustreated material is next heated at elevated temperatures, for example 500 to 700 F, for a period of time whichmay conveniently range from 0.5 to 2 hours. Separation from excess acid without washing inherently or unavoidably leaves unreacted'acid on the coated metal which is present during the calcination step. After adjustment of the particle size to the desired value, which is frequently about 5 to 15 mesh, the catalyst is ready for use. This catalyst is probably composed of the free metal, the metal phosphate in the form of pyrophosphate, and P205.

In reacting the metal with the acid, magnesium will be found'so active that it is difiicult to stop the reaction and retain some free metal. The metals below hydrogen in the electromotive force series do not react directly with the acid, hence a pre-treatment of same to form a coating re- -active with acid is required. This usually comprises treatment with an oxidizing agent. For example, hot chlorine gas will oxidize the metal surface and form the chloride, which is readily reac- Either free oxygen, preferably in the form of air, or a nitrogen oxide compound such as heated N02 or 'HNOsvapor, is suitable, giving the metal oxide, or sometimes the nitrate, as coating. The thus- -treated particles of metal are then reacted with 'oneof the stronginorganic oxygen-containing acids having a non-volatile anhydride and the treatment continued as described to form the peroxide, or with hydrogen sulfide to form silver sulfide followed by oxygen treatment to form the oxide. Certain metals above hydrogen in the electromotive force series, especially cadmium and lead react with oxygen-containing acids only very slowly, and this reaction may be accelerated to practical rate by adding a trace of another metal, such as copper or copper sulfate or a ."metal such as platinum or other metal to set up a galvanic cell. After visible evolution of hydrogen ceases the excess acid is drained and the material calcined as described above.

'Qthercatalysts are prepared by effecting admixture of the metal directly with the acid an- "hydride, with or without the salt of the metal and acid. For example, phosphorus pentoxide is sublimed onto particles of spongy zinc. As another example, chromic acid is mixed with iron chromate, the mixture calcined and powdered and aolmixed with powdered iron metal.

In the preferred embodiment of the present in- 'vention, an organic mixture containing an organic fluorine compound is passed, in either the liquid oryapor phase, through a treating zone containing both a powdered or a granular catajlytic defluorinationfmaterial and a hydrogen fluoride-sorption medium. This treating zoneis total layers are used in the treating zone. I

usually arranged in such a manner that the catalyst and the sorption medium are in alternate layers. By such an arrangement the first catalytic layer establishes a decomposition equilibrium reaction and the subsequent sorption layer upsets this equilibrium by removing liberated hydrogen fluoride; then the next catalytic layer reestablishes the decomposition equilibrium 'by decomposing at least a portion of the remaining organic fluorine compound. Each following. catalytic and sorption layer actsin a similar manner until substantially all of the organic fluorine compound is decomposed. l

Another embodiment, which may also be practiced, is the arrangement of the catalyst and sorption medium in successive zones rather than in a single zone; thus, the catalyst will be maintained in one separate zone or column and the sorption medium will be maintained in a second and successive zone or column, through which the organic mixture passes, respectively. Still another arrangement may be followed by supporting alternatelayers of catalyst and sorption medium in a sorption column in such a manner that free space exists between the supported layers. This arrangement is especially desirable since the tendency for channelling of a liquid hydrocarbon stream through the powdered or granular contact material is minimized; The number of layers or zones which will be suitable for removal of the organic fluorine compound depends upon several factors such as the type of catalytic material, the type of sorption medium, the conditions of temperature and pressure, and the depth of the catalytic and sorption beds; but such conditions and the number of successive layers or zones may be easily determined by trial.

In general, it will be sufficient to use layers of In a somewhat less preferred embodiment of the present invention the catalyst and sorption medium may be admixed together in a treating zone in a more or less uniform manner and' the organic mixture contacted with the uniform mixture of catalyst and sorption medium. The arrangement of alternate layers of separate zones for each contact material is preferred in order to facilitate recovery of the sorbed hydrogen fluoride, if desired, and also since the contact of liberated hydrogen fluoride with the catalyst may substantially decrease the catalytic activity thereof by the conversion of the hydrogen fluoride to the corresponding metallic fluoride. Such conversion to the metallic fluoride consumes both the catalyst and the hydrogen fluoride so as to decrease the activity of the catalyst and hinder the recovery of hydrogen fluoride, although in some cases the metal fluoride will becatalytically active for dehydrofluorination. f

The acid-treated metals of the present invention are particularly adaptable to the process disclosed herein in which a fluid containing fluorine compounds is contacted alternately or simultaneously with a. defluorination agent and with a hydrogen fluoride sorption material, inasmuchas an organic mixture have been found to comprise charcoal, dehydrated bauxite, granular metal oxides such :as alumina, chromium oxide, and 151a hydrated metal oxide gels and the like. Materials which are capable of sorbing hydrogen fluoride and which involve a chemical reaction to form a decomposable salt are es ecially desirable- Such :sorbent materials may comprise fluorides .Of the alkali and alkali earth metals, osueh as sodium'fluoriele or potassium fluoride, whichicrm the addition compound of the type if desired, the hydrogen fluoride :may he recovered from the double salt :by heating directly .Q,r ;by passing hot gases over the :sorption medium. Nitrogen bases and metal 'salts that .form acid fluorides are also :suitable :for sorption of the liberated hydrogen fluoride.

flbviously both the catalyst and sorption. :me diumzmayibe-sunportedon various inert ima-teriarls well known :to those skillediin the art without fielzparting :fromthe :scope of this invention.

-In:practicing the :pref erred embodiment :of this about "56 inches and :the number of layers :may

UG ab-GlItiIO rtozaboutl25; the actual :thicknessgand number oflayerswillzdenend upon-the conditions :of operationiand .uponithe particular cataiyst; and sorption'mediumused. sSuchaconditiQns set i f above are r not :.-limiting .to :the scope 10f hlS lvention, lout are those "which have heen fnuhd preferable inzgeneraliofor removing substantially 5311501 the (organic l fluorine icomponnds from th hydrocarbon mixture without efiectingext A chemical changes the hydrocarbons themselves. Various other conditions may :he .z fliir d appropriate by trial.

:In the Leasewhere thecatalytic agentvand t e 'ssorption medium areinsepanatezones-or col mns asomewhat difierent conditions of temc retu e, pressuiie,.etc.may :belused foreac-h columnduring :defluorination. Thus, rclatiyely::h-i h-tsm pera-tures and. low :pressures :may 'be used the c'atalyst:::zone, while relatively ew temp atures and hiehmressures may-be used in the-.sorption zone. However, due to economi r as n -it may Joe more desirable to maintain substantially the same conditions in both the catalytic and sor-ption It :is :preferredthat the hydrocarbonematerial subjected to treatment iiitgaccoiidancerwith this sorbs' the liberate h drog n flu ride hareoa this material ma he egener- Mme sup rhe ted st am o o her ot s utanea at a emp ature r m about roll o a out $.00 pre era about 1 o 00 and at app oxima y atmosp ri pr ssure t rou h or con act w th the sorp ien medium.-

a ma e ial! uch as s di or potas ium fluo id w ich orms eddit re som sound with he l berated hyd oeen fluorid is used as the s ptionlme um, t e tem e ature o h regenera n eels, s ch team bu an eta, .is. vfr m about 1 0 to abou 0" s er ably f om about 609 to about 1-H, and he pressure is ap ox m ely atm sp t may also nrefe red to ooerate the-regen r ion cycl at same p essure th emotion c cle, us (use of el va ed p sure tor IQEQDBP. c.

indie-scon orth sin ent on R g neration :oi Joe sor tion mediu ma be accomplished also by hea in the s t on med um di tl w thout P ssi g a h t gas hrough t e medium- Upon heatin the sorpti n medi m u ing esenera-tion, whe h by di ect means r by the us of t gases, vamorous hydrogen fluo de is liberated wh ch ma 'b reco red by m th tam lia it tho e sk l ed i the a .l pe i when ese eratineeas, such eshute a used, the hydro (fluo ide m y be e .=o ed ifIlQm the resul in seous mix u .by co densnsthega eousr xtu een i e. hal s d st l n the condensa to recove the hydrogen fluoride.

A t ou t is invent on h aspli d th a vanta ein many modificatio tcth remo a o either orga 1.6 ino gan c fluc in 011 pounds fro bo h-o anic and i trrsa s field mix e rart ularb nefit of it ha e ee 'rea hes in conne t on wi h the alk etion o W- ilin is arafiins with-low-h ili a oleficsin he ln esence of .a fluo in -co t inin a ky s on :catalyst Thema ner f conduct n de uo ine- =.-tien-.an /or-.dehad ofiuerin tiqn r actions in the rresenee Qf he instan e ta ys me be sim a :t athe e ods etiior h; 37- Pa ent 24:81208 referred t above,

The following xa p es i u at t e tonerrabilit :cf th pres nt 1 in e n and also sh w the :efiect e ess ofr he pre erred deliaminati sca alystfor use i his inv nt on- EXAMPLE I v-tA min v-sh ihes .e o t 0- 0 nch thic Msre Jacd. in b aker and er d w th 8 pe c nt Ql hOPhQSPh-Oric acid- Whe evolut on 1 hyd o enhad-appar nt yceas th sol d et ri liwas rem ved from th h a se and the pa ticles were broken tohapproximately the siz e of ,theoriginal havin s. Ilhe. solid (material vwas then placedimanelectrically,- heat-ed steel tube in which it was \slowly heate i t -2 F- a mainta nec'l atthist mpe ature for one hour. it was then removed, cooled, and educed to a. par- 'ticleu-size sufiic ently mal t a an -Ihesh screen.

ewhich isobutane was alky-iated with butylenes,

was contacted at 250 F. and-400 p. s. i.in-a continuous :flow system with. the catalyst prepared ;as.;-descrihed ineExample'i. 'E'The data obtained ithe sorption"mediumis a.nonrreactiveomaterial2 5 arezgivenin'TablefI.

Table I DEHYDROFLUORINATION WITH PHOSPHORIC ACID-TREATED ALUMINUM F Compounds, wt. percent Space Veloc- Cumula- Cumulative F retive Time, Vol. Treated/ 2 gg gf g gg moved, our V01. Catalyst catalyst percent Org. F HF Org. F III EXAMPLE III the fluorine removal was 78 per cent, whereas in A similar hydrocarbon material was contacted at 212 F. and 250 p. s. i. in the same flow system, 9 with aluminum shavings, the surface of which had been etched with dilute hydrochloric acid and washed free of acid. The data obtained are given in Table II.

the case of the HCl-etched aluminum after treatment of 497 volumes of feed at 1.1 to 2.5

J) space velocity the latter catalyst was removing only about 23 per cent of the organic fluorine. Although the data shown in Table II were obtained at 212 F., whereas the data presented Table II DEHYD ROFLUORINATION WITH ETCHED ALUMINUM F Wt. percent Space Velocgg% g ,a r f gg g ity, 'q. Before Treat- After Trcat- R re Hour Cam] St vol/vol. ment ment moved, y catalyst/hr. percent Org. F HF Org. F HF Comparison of the data in Tables I and II clearly shows the superiority of phosphoric acidtreated aluminum as a catalyst for removal of organic fluorine. The etched aluminum, after treatment of 1340 volumes of hydrocarbon containing organic fluorine, removed only 17 per cent of the organic fluorine, whereas, after treatment of 1345 volumes, the phosphoric acidtreated aluminum removed 63 per cent. It will also be noted that at the end of each run the etched aluminum metal had only a little less than a third of its original activity, that is it was removing 17 per cent fluorine, whereas at the start it removed 55 per cent fluorine, while the phosphoric acid-treated aluminum metal retained sixty per cent of its original activity. Further comparison shows that in the case of the phosphoric acid-treated catalyst, after treat- EXAMPLE IV Fluorine-containing hydrocarbon alkylation efliuent similar to those treated in Examples 11 and III was contacted at 250 F. and 400 p. s. i. in the same equipment and in the same manner with freshly prepared aluminum shavings etched with dilute H01 and then Washed free of acid.

ment of 455 volumes of feed at 4.1 space velocity, The data obtained are presented in Table 111.

Table III DEHYDROFLUORINATION WITH ETOEED ALUMINUM F wt. percent Cumulative Space Velo- Fluorine Cumulative V01. city, liq. Before treat- After treat- Re- Tune, Hour Treated/Vol. vol/vol. ment ment moved, Catalyst catalyst/hr. percent Org. F HF Org. F HF Although this invention has been described with reference to alkylation in particular, and the examples have. used particular catalysts, it is evident that the invention in general may be used in connection with various other processes for the removal of fluorine compounds from a fluid mixture. Furthermore, various modifications of equipment, process flow, and specific catalysts and the preparation thereof, will be obvious to those skilled in the art without departing from the scope of this invention.

The methods disclosed herein may be employed in the preparation of catalysts which are particularly adapted for use in the defluorinating of organic materials as described above. However, the catalysts of this invention are likewise adaptable to use in various other chemical reactions, particularly those catalyzed by phosphorus pentoxide and/or metal phosphates including pyrophosphates, such as polymerization of unsaturated hydrocarbons, and others described hereinbelow.

Unsaturated hydrocarbons, particularly the C2 to C4 gaseous olefins, may be polymerized by passing same in contact with my catalysts at temperatures within the range of 250 to 650 F., and at superatmospheric pressures preferably from 200 to 1000 pounds per square inch. Flow rates are chosen to give the desired extent of polymerization, and generally range from 1 to 10 liquid volumes feed per volume of catalyst per hour or 50 to 6000 volumes of gas per volume of catalyst per hour. The reaction mixture may consist of a single pure olefin or a mixture of olefins, but will preferably also contain inert diluents such as light paraffin hydrocarbons. A mixture of isobutylene with normal butylenes and butane may be subjected to co-polymerization, for example. A somewhat related operation involves the stabilization of a cracked gasoline against gum formation by treatment with my catalysts at 100 to 300 F. and to 300 p. s. i., effecting polymerization of diolefins and other highly unsaturated materials while leaving the desired mono-olefins relatively unaffected.

The alkylation of aromatic hydrocarbons may also be effected, employing the catalysts of the present invention. Thus, benzene, toluene or naphthalene may be reacted with a methylating agent such as methyl alcohol or dimethyl ether at 300 to 500 C. and a pressure of 1 to 300 atmospheres with a contact time which will vary from 1 to 100 minutes, depending upon the temperature and other reaction conditions, the longer contact times being employed with the lower temperature and vice-versa. At least one mol of the aromatic hydrocarbon per mol of methylating agent should be employed, and preferably the former is in considerable excess over the latter. Other alkylating agents, particularly ethylene and higher olefins, are effective to produce the corresponding alkylated aromatic hydrocarbons. The mono-alkyl derivative is formed to the greatest extent although diand higher poly-alkyl derivatives are present in the reaction mixture to some extent, and may be made the predominant product if desired by increasing the contact time and/or decreasing the ratio of aromatic hydrocarbon to alkylating agent. As part of the same over-all process to ,form mono-alkyl aromatics, or as a separate process, polyalkyl aromatic hydrocarbons may be dealkylated by reaction with benzene or other aromatic whereby alkyl groups are transferred from the polyalkyl aromatics to the latter. Preferably at least one mol of benzene per mol of poly-alkyl 'aromatic is employed and this quantity may range up to 10 mols per mol of poly-alkyl aromatic; temperatures of 300 to 600 C. and pressures of 1 to 200 atmospheres are suitable.

Other processes in which my catalysts find particular utility is in the dehydration of alcohols to form the corresponding olefins, in which an alcohol, preferably having from 2 to 5 carbon atoms per molecule, is contacted with the catalyst at 300 to 500 C. at about atmospheric pressure, employing a liquid space velocity from 1 to 25 volumes per volume of catalyst per hour. Conversely, olefins are hydrated to form the corresponding alcohols, as by passing one mol of olefin together with from 0.5 to 5 mols of steam over the catalyst at to 300 C. and 20 to 100 atmospheres. A reaction time from 10 minutes to two hours is used, the exact time depending upon the reactivity of the olefin and the extent of conversion per pass desired, as well as the activity of the particular catalyst employed.

As another example of the utility of the catalysts of this invention, methane may be utilized to form methanol and formaldehyde as principal reaction products, by passing oxygen admixed with a molar excess of methane over the catalyst at 60 to 1000 F. at a pressure of 200 to 750 pounds per square inch.

In any of the foregoing conversion processes in which the catalyst becomes deactivated by deposition of carbonaceous material thereon, effective reactivation of the catalyst may be accomplished by stopping the flow of reactants thereover and passing an oxygen-containing gas through the catalyst mass at conditions of oxygen concentration and flow rate controlled to avoid excessive temperature in the catalyst whereby the carbonaceous matter is removed from the catalyst by oxidation and the catalyst put in condition for reuse. Other specific uses of the catalyst described and claimed herein will be apparent to one skilled in the art.

I claim:

1. A catalyst consisting essentially of at least one metal of the group consisting of Al, Cd, Zn, and Cu coated with a solid material obtained by calcining a mixture of an acid of the group consisting of oxygen-containing acids of phosphorus, chromic acid, and tungstic acid and the reaction product of said metal and said acid.

2. A catalyst according to claim 1 in which said acid is concentrated phosphoric acid.

3. A catalyst according to claim 1 in which said acid is chromic acid.

4. A catalyst according to claim 1 in which said acid is tungstic acid.

5. A method of preparing a catalyst which comprises contacting at least one metal of the group consisting of Al, Cd, Zn, and Cu with an excess of an acid of the group consisting of oxygen-containing acids of phosphorus, chromic acid, and tungstic acid for a time sufiicient to eifect substantial reaction between said acid and the surface of said particles, removing thustreated particles from the bulk of said acid so that the particles are coated with the reaction product and the residual acid, and then calcining the so-removed particles to form said catalyst by forming a hard coat of reaction product on the metal.

6. A method of preparing a catalyst useful in decomposing organic fluorine compounds, which comprises contacting particles of aluminum metal with an excess of orthophosphoric acid until vis- 19 ible evolution of hydrogen subsides, separating the bulk of the excess acid so that the particles retain some residual acid, and calcining the resulting particles to form said catalyst by forming a hard coat of reaction product on the metal.

7. The method of claim in which said metal is cadmium.

8. The method of claim 5 in which said metal is zinc.

9. The method of claim 5 in which said metal is copper.

10. The method of claim 5 in which said acid is an acid of phosphorus.

11. A method of preparing a catalyst which comprises reacting particles of aluminum with 75 per cent phosphoric acid in excess so that after evolution of hydrogen ceases, the aluminum is coated with acid and reaction product; and calcining the resulting aluminum coated with a mixture comprising the acid and aluminum phosphate at an elevated temperature so as to dehydrate and harden the coating.

12. A catalyst according to claim 1 in which the metal is aluminum.

13. A catalyst according to claim 1 in which the metal is aluminum, the acid used is 75 per cent phosphoric, and calcination is efiected in the range of 500 to 700 F.

14. A catalyst consisting essentially of particles of at least one metal of the group consisting of Al, Cd, Zn, and Cu coated with a solid material obtained by calcining a mixture of an acid of the group consisting of oxygen-containin acids of phosphorus, chromic acid, and tungstic acid and the reaction product of said metal and said acid.

15. A catalyst consisting essentially of particles of at least one metal of the group consisting of Al, Cd, Zn, and Cu coated with a solid material obtained by calcining a mixture of a liquid oxygen-containing acid of phosphorus and the reaction product of the metal and said acid.

16. A catalyst according to claim 15 in which said acid is concentrated phosphoric acid.

17. A catalyst according to claim 16 in which said metalis A1,

18. A catalyst according to claim 16 in which said metal is Cd.

19. A catalyst according to claim 16 in which said metal is Zn.

20. A catalyst according to claim 16 in which said metal is Cu.

21. A method of preparing a catalyst which comprises contacting particles of a metal of the group consisting of Al, Cd, Zn, and Cu with an excess of an acid of the group consisting of oxygen-containing acids of phosphorus, chromic acid, and tungstic acid for a time sufficient to efiect substantial reaction between said acid and the surface of said particles, removing thustreated particles from the bulk of said acid so that the particles are coated with the reaction product and the residual acid, and then calcining the so-removed particles to form said catalyst by forming a hard coat of reaction product on the metal.

22. A method of preparing a catalyst useful in decomposing organic fluorine compounds, which comprises contacting particles of a metal of the group consisting of Al, Cd, Zn, and Cu with an excess of orthophosphoric acid until visible evolution of hydrogen subsides, separating the bulk of the excess acid so that the particles retain some residual acid, and calcining the resultin particles to form said catalyst by forming a, hard coat of reaction product on the metal.

JACK F. EBERLE.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,199,180 Laughlin Apr. 30, 1940 2,339,929 Houghton Jan. 25, 1944 2,364,970 Gwynn Dec. 12, 1944 2,434,850 Hochwalt et al Jan. 20, 1948 2,434,888 Rust et al. Jan. 20, 1948 2,462,938 Bludworth et al. Mar. 1, 1949 2,467,484 Kanhofer Apr. 19, 1949 2,501,846 Gifford Mar. 28, 1950 2,525,107 Whiting et a1. Oct. 10. 1950 

1. A CATALYST CONSISTING ESSENTIALLY OF AT LEAST ONE METAL OF THE GROUP CONSISTING OF AL, CD, ZN, AND CU COATED WITH A SOLID MATERIAL OBTAINED BY CALCINING A MIXTURE OF AN ACID OF THE GROUP CONSISTING OF OXYGEN-CONTAINING ACIDS OF PHOSPHORUS, CHROMIC ACID, AND TUNGSTIC ACID AND THE REACTION PRODUCT OF SAID METAL AND SAID ACID. 